Sulfurized dyes and process of making same.



UNITED STATES PATENT OFFICE.

HEINRICH HEIMANN, OF DESSAU, GERMANY, ASSIGNOR TO ACTIEN GE SELLSCHAFT F'UR ANILIN FABRIKATION, OF BERLIN. GERMANY.

No Drawing.

Specification of Letters Patent.

Application filed October 16, 1912.

S rial No. 726,123.

To all whom it may concern Be itlmown that. I, Hemmer! Hnnmi-zzs, a citizen of the German Empire, residing a Dessau, Germany, my postollice address being Friedrich-Schneider strasse 63, Dessau, Germany, have invented new and useful lmprovemenfs in Sulfurized Dyes and lrocesses of flaking Same, of which the following is a specification. v

In my copending application Serial l\o. 726.12]. I describe and claim generally new sulfurized dyes fast ilr'iifli-lllngfllfll to chloriu which may he ohtained by acting: wilh a sull'urizing agent upon a 'l-hy(lr irl -diarylamin in which only the. l-hydronyaryl group IS capable of assuming the paraquinoid form.

Now in my present application I claim a. special class of these new dyes which deri 'e from those of such -l-h vilrox liarylannn in which the lmosition is occupied by an alhoxy group or from their derivatives in which the two henzenenuclci contain vfurther univalent substituents such as a halogen, an allryl or alkoxy group, a carboxylic group, etc, the aulfonic group being excepted.

In producing the new sulfur dyes according to this inv'ention I may also use as parent material the corresponding lhio compounds,

the corresponding derivatives of biodiphenylumin; thus for instance instead of sl-l:ydroxyl-methoxydiphenylamin I. may employ the 4" hydroxy-4' methoxythiodiphcnylamin.

The. following example may serve to illus- -lrate my invention, the parts being by weight: 30 parts of 4-hydroXy-l'-1nethoxydiphcnylamin are introduced into a solution prepared from 90 parts of crystallized sodium sulfid, 90 parts of water and 72 parts of sulfur. The mass is then boiled during about 24 hours at the reflux condenser, whereupon 45 parts of crystallized sodium suliid dissolved in about, 1500 parts of water are. added. From the resulting mass the dye is isolated by introducing a current of air, filtering, washing and drying. The new dye thus obtained produces on cotton without; a mordant in a bath containing an alkali sulfid red-brown tints with a blue cast which possess an excellentfastness to washing and are fast to chlorin.

The new dyes derived from a -hydroxy- J-allroxydiphenylamin representin the dry state when pulverized dark brown powders which are very difiicultly soluble'in alcohol,

I glacial acetic acid, benzene and chlorobcu- Zeno; hey are more or less dillicullly soluble in nilrobcnzcne, anilin and pyridin. ln cuneentratcd sulfuric acid and in 25% fuming sulfuric acid they dissolve, generally speak lug. to blue to violol' solutions which remain unaltered on the addition of boric acid huta re gradually dccolorized on lhe addition of aluminium powder.

The new dyes are also capable of being dyed from a hydrosulfite vat giving, generally speaking, yellow vat from which cotton is dyed, generally speaking, red-brown tints.

ll; obvi us to those skilled in the art that my invention is not limited to the f0regoing example or to the delails given therein. Thus for instance instead of 4--hydr0Xylmctlioxydiphenylamin the corresponding clhoxy derivative may be employed; furthermore the new dyes may also he prepared by healing the parent material with sulfur alone.

It may also be stated that the proportions of the ingredients as well as the temperature of rea tion or the duration of heating may be altered within wide limits without departing from the scope of my present in vention.

'Having now described my invention and the manner in which. it may be performed what I. claim is 1. The manufacture of new sulfurized dycs'fast to washing and to chlorin by acting with a 'snlfurizing agent upon a it-hydroxvmlkoxydiphenylamin contaihing no sulfonic group and having the following nucleus:

l l I I 0s o cNn-o e on in which diagram R means an alkyl-group. 2. The manufacture of new sulfurized dyes fast to washing and to chlorin by acting with a polysulfid upon a i-hydroxyalkoxydiphenylamin containing no sulfonic group and having the following nucleus:

| l in which diagram R means an alkyhgroup. 3. The manufacture of new sulfurized dyes lalci'itcd May 26, 1914.

' a polysulfid in the presence of subsie fast to washing and m chlerin by acting 1* being a liquid at the temperatures prevail ing during the reaction upon 4-ell:oxydipl1enyl11min containing no sul ionic gieup and the inhuman; nucleus:

in which diagram R means an 4. The manufacture of new suliurized dyes, fast to washing and to chloriu, y seiing with sulfurizing agent upon hy droXy-4" methoxydiphenylamin.

5. The manufacture of a new eulfurizcd dye, fast to Washing and to ohloriulw act ing with e. polys'ulfid tapes i-hyuso iethoxydiphenylamin.

6. The manufacture of a: new sulfur" dye fast to washing; and to c ing with a polysulfid in suitable liquid 11 p011 l-llydfl diphenylamiii.

7 As new articles of manufacture @ilie KW?! sulfurized dyes, fast to Washing and chlorin, derived from a i hydroxyiaikoz" diphenylaniin, which new dyes in ilie 2h state when pulverized represent der powders which are very (lifficultly soluble in alcohol, glacial acetic acid, benzene and chlorohenzene and which more or lee": difiicultly soluble in ni'u'oliaeiwefieeri and pyridin, these new dyes d 011 eoneeurated sulfuric acid and 253 1; fm': sulfuric acid, generally speaking, to x e to Violet solutions which rennin unaltered on the addition of boric acid but are gi'uduslly mkylgreu m eddii ion of aluminium new dyes producing on item from a dyebath consulfid, qenerally speaking, and which new dyes are being dyed from a hydr0- ding, generally speaking, a

finish eat-ton is dyed, gen- -brown tints.

ertiei of manufacture a new 'e which may be obtained by slysulfid upon -hydroxyi gland? which new dye in the pull deed is a dark red- Niel acetic acid, beneue to a red to blue-red miuoie in nit-robenzene, 7 Lo blue-red solution, in concentrated sulfuniing sulfuric acid remains unaltered acid but is gradueddition of aluminicii new dye produces el-bath containing an i tints wiih a blue cast 5o washing and fast to 'JQW dye is also capable F osulfi'ce vat yieldiii-2h cotton is dyed A xii ii blue cast.

hereof I have signed my on. in the dresence of HEIMANN. 

